CN105536447B - Application of fluorine-doped perovskite type membrane in oxygen separation - Google Patents

Application of fluorine-doped perovskite type membrane in oxygen separation Download PDF

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CN105536447B
CN105536447B CN201610025622.9A CN201610025622A CN105536447B CN 105536447 B CN105536447 B CN 105536447B CN 201610025622 A CN201610025622 A CN 201610025622A CN 105536447 B CN105536447 B CN 105536447B
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oxygen
film
application according
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membrane
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CN105536447A (en
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金万勤
朱佳伟
刘郑堃
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Nanjing Tech University
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Nanjing Tech University
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Abstract

The invention relates to an application of a fluorine-doped perovskite type membrane in oxygen separation; the membrane material is of the general formula AxA’1‑xByB’1‑ yO3‑FγThe perovskite crystal type oxyfluoride of (1), wherein the number of oxygen lattice defects is A, A', and the oxygen lattice defect number is any one element of Ce, Pr, Nd, Ca, Sr, Ba and La; b and B' are any one element of Co, Fe, Nb, Ta, Mo, W, Sc, Ti, Zr, Sn and Sb; x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; 0<Gamma is less than or equal to 1. The oxygen permeable membrane material provided by the invention can greatly improve the oxygen permeability of the material by doping non-metallic fluorine, maintains the high stability of the material under low oxygen partial pressure, has excellent medium and low temperature performance, is suitable for long-term operation of medium and low temperature oxygen separation, and meets the requirements of industrial application.

Description

A kind of application of the Ca-Ti ore type film of Fluorin doped in oxygen separating
Technical field
The invention belongs to the design and development field of mixed conductor compact oxygen permeable membrane, the calcium titanium of especially a kind of Fluorin doped Application of the ore deposit type film in oxygen separating.
Background technology
Mixed conductor material be it is a kind of can the inorganic ceramic membrane material of conduction oxonium ion and electronics simultaneously, extensively should at present Prepared for pure oxygen, the multiple fields such as SOFC and membrane reactor.Using mixed conductor oxygen permeable membrane to oxygen The selectivity of ion 100%, the preparation of pure oxygen can be applied to.Passed in addition, being substituted with mixed conductor oxygen permeable membrane technology Such as cryogenic separation of the spatial division technology of system, nearly 1/3rd investment and running cost can be saved.However, mixed conductor Oxygen permeation The ultimate challenge that membrane technology faces at present is middle low-temperature zone mixed conductor material Oxygen permeation flux is relatively low and less stable.
At present, lot of domestic and international research group is all being directed to opening for the mixed conductor oxygen permeable membrane material of high osmosis Hair.They by A positions either B positions doped metal ion or change metal ion stoichiometric proportion come the property to material Matter is adjusted, and have developed the material of many excellent performances.But this kind of material is relatively low in the flux of middle low temperature, it is difficult to Meet the requirement of industrial applications.Therefore, exploitation is a kind of has high permeation flux under middle low temperature, and has excellent length The mixed conductor membrane material of phase stability is of great significance for the industrial applications tool of mixed conductor membrane.
The content of the invention
A kind of Ca-Ti ore type film of Fluorin doped is provided in oxygen the invention aims to improving prior art deficiency Application in separation.The Ca-Ti ore type film of Fluorin doped not only has high permeation flux under middle low temperature, and with excellent Stability, it is suitable for long period of operation.
The technical scheme is that：A kind of application of the Ca-Ti ore type film of Fluorin doped in oxygen separating.
It is preferred that the Ca-Ti ore type film of above-mentioned Fluorin doped, its material formula is AxA’1-xByB’1-yO3-δFγPerovskite crystal formation Oxyfluoride, wherein δ is oxygen lattice defect number, A, A ' be any one element in Ce, Pr, Nd, Ca, Sr, Ba or La；B、 B ' is any one element in Co, Fe, Nb, Ta, Mo, W, Sc, Ti, Zr, Sn or Sb；0≤x≤1,0≤y≤1；0<γ≤1.
It is preferred that the Ca-Ti ore type film of above-mentioned Fluorin doped is prepared by following methods, it is comprised the following steps that：
A. weigh raw material according to the stoichiometric proportion of material to be mixed, roasted dry mixture after well mixed Burning processing, membrane material is obtained after products therefrom grinding；
B. the green compact of film are made by being molded for above-mentioned membrane material；After the green compact of film heat up and sintered in high temperature furnace, take out Cooling, produces film.
Raw material described in step A is respectively containing metal element A, A ', B, B ' carbonate, containing metal element A, A ', B, B ' oxide powder or containing metal element A, A ', B, B ' fluoride powder.
The method mixed in preferred steps A is addition solvent ball milling 3-10h, rotating speed 400-550rpm.
Sintering temperature in preferred steps A is 800-1200 DEG C, roasting time 5-10h.
The particle diameter of membrane material is 200nm-10 μm after being ground in preferred steps A.
It is preferred that described molding mode is single shaft pressure, plasticity extrusion or phase inversion shaping.
It is 1-5 DEG C/min that heating rate is sintered in preferred steps B, and sintering temperature is 1000-1300 DEG C, sintering time 5- 20 hours, rate of temperature fall was 1-5 DEG C/min.
Film prepared by the present invention cannot be only used for the oxygen separating process of middle efficient cryogenic, can be also used for membrane catalytic reaction Process.
Beneficial effect：
For mixed conductor oxygen permeable membrane, the most important problem that presently, there are is exactly that membrane material leads in middle low-temperature zone Measure relatively low, less stable.Therefore, it is to achieve the key of industrial applications to improve the flux of film and stability.At present, state Inside and outside many research groups are all in the exploitation for the mixed conductor membrane material for being directed to high osmosis.But the membrane material developed It is still limited in the permeance property of middle low-temperature zone.Therefore develop it is a kind of there is high permeation flux under middle low temperature, and have The mixed conductor membrane material of excellent long-time stability is of great significance for the industrial applications tool of mixed conductor membrane.
In the present invention, the perovskite-type material of Fluorin doped is used for into mixed conductor membrane can obtain good oxygen separating effect Fruit.Element F with highest electronegativity enters perovskite material, reduces the chemical bond energy between B position ions and oxonium ion, reduces The migration energy of oxonium ion, so as to improve the migration of oxonium ion and Oxygen permeation flux, so the presence of F elements has beneficial to raising calcium The oxygen permeability of titanium ore material.The material not only has high permeability, and the apparent activation energy during Oxygen permeation Than relatively low, therefore material becomes apparent in the advantage of the oxygen permeability of middle low-temperature zone, suitable for the oxygen separating of middle efficient cryogenic Process, and middle efficient cryogenic catalysis film reaction.
Brief description of the drawings
Fig. 1 is the Ba prepared by embodiment 10.5Sr0.5Co0.8Fe0.2O3-δF0.1Chip film green compact it is 8 small in 1050 DEG C of sintering When after surface microstructure figure；
Fig. 2 is the Ba prepared by embodiment 10.5Sr0.5Co0.8Fe0.2O3-δF0.1After 8h being calcined in 900 DEG C of air atmospheres X-ray diffraction curve map；
Fig. 3 is the Ba prepared by embodiment 10.5Sr0.5Co0.8Fe0.2O3-δF0.1Prepared chip film is at different temperatures Oxygen permeability figure；
Fig. 4 is the Pr prepared by embodiment 20.2Sr0.8Fe0.9Nb0.1O3-δF0.4Prepared hollow-fibre membrane shape appearance figure；
Fig. 5 is the BaCo prepared by embodiment 40.9Nb0.1O3-δF1The oxygen permeability figure of prepared film.
Embodiment
Illustrate embodiments of the invention below in conjunction with the accompanying drawings.
Embodiment 1
Material Ba of the present invention is prepared with solid reaction process0.5Sr0.5Co0.8Fe0.2O3-δF0.1Exemplified by, by the stoichiometry of material Than by SrCO purchased in market3, BaCO3, Co2O3, Fe2O3, and SrF2After powder mixing, ethanol is added, is placed in wet film in ball mill 6h, rotating speed 450rpm, then dried in still air, dry powder is calcined 8h in 900 DEG C of air atmospheres, it is ground The Ba that particle diameter is about 1 μm is obtained afterwards0.5Sr0.5Co0.8Fe0.2O3-δF0.1Powder.
Film green compact are made in powder under 200MPa uniaxial tension, and it is 2 DEG C/min to control heating rate, and film green compact are existed 1050 DEG C of sintering cool to room temperature, i.e., chip film (diaphragm thickness 1mm) after 8 hours with 2 DEG C/min speed.Film Surface microscopic figure such as Fig. 1.It can be seen that film surface has clearly boundary, and film surface compact imporosity.
By Ba0.5Sr0.5Co0.8Fe0.2O3-δF0.1Powder carries out X-ray diffraction test, as seen from Figure 2, Ba0.5Sr0.5Co0.8Fe0.2O3-δF0.1Material has complete Perovskite Phase structure, and the Perovskite Phase of material is not sent out before and after doping Raw obvious change.
To material Ba0.5Sr0.5Co0.8Fe0.2O3-δF0.1Prepared chip film carries out the oxygen permeability under different temperatures Test.And and Ba0.5Sr0.5Co0.8Fe0.2O3-δCompare.As a result Fig. 3 is seen.
As seen from Figure 3, doping F elements can significantly improve Oxygen permeation flux of the material in middle low-temperature zone, at 600 DEG C Oxygen flux reached 0.3mlmin-1cm-2, it is adapted in oxygen separating and the application of film reaction field.
Embodiment 2
Material Pr of the present invention is prepared with solid reaction process0.2Sr0.8Fe0.9Nb0.1O3-δF0.4Exemplified by, by the stoichiometry of material Than by SrCO purchased in market3, Pr2O3, Nb2O5, Fe2O3, and FeF3After powder mixing, ethanol is added, is placed in wet film in ball mill 3h, rotating speed 400rpm, then dried in still air, dry powder is calcined 10h in 1200 DEG C of air atmospheres, through grinding The Pr that particle diameter is about 5 μm is obtained after mill0.2Sr0.8Fe0.9Nb0.1O3-δF0.4Powder.
Hollow-fibre membrane green compact are made by the method for inversion of phases in powder, and it is 4 DEG C/min to control heating rate, by film green compact After 1300 DEG C sinter 15 hours, room temperature is cooled to 4 DEG C/min speed, produces hollow-fibre membrane, as shown in figure 4, film Dense layer thickness be 50 μm
By Pr0.2Sr0.8Fe0.9Nb0.1O3-δF0.4Powder carries out X-ray diffraction test, it is found that it has complete perovskite Phase structure, obvious change does not occur for the Perovskite Phase of material before and after doping.
Pr0.2Sr0.8Fe0.9Nb0.1O3-δF0.4Hollow-fibre membrane carries out the oxygen permeability test under different temperatures.From test As a result as can be seen that doping F elements can significantly improve Oxygen permeation flux of the material in middle low-temperature zone in, lead in 650 DEG C of oxygen Amount has reached 0.6mlmin-1cm-2, it is adapted in oxygen separating and the application of film reaction field.
Embodiment 3
Material La of the present invention is prepared with solid reaction process0.9Ca0.1Co0.4Mo.6O3-δF0.7Exemplified by, by the stoichiometry of material Than by CaCO purchased in market3, La2O3, Co2O3, MoO3, and CoF3After powder mixing, ethanol is added, is placed in wet film in ball mill 8h, rotating speed 550rpm, then dried in still air, dry powder is calcined 5h in 1000 DEG C of air atmospheres, through grinding The La that particle diameter is about 200nm is obtained after mill0.9Ca0.1Co0.4Mo.6O3-δF0.7Powder.
Tubular membrane green compact are made by plasticity extrusion method in powder, and it is 5 DEG C/min to control heating rate, and film green compact are existed 1200 DEG C of sintering cool to room temperature with 5 DEG C/min speed, produce tubular membrane after 20 hours
By La0.9Ca0.1Co0.4Mo.6O3-δF0.7Powder carries out X-ray diffraction test, it is found that it has complete Perovskite Phase Structure, obvious change does not occur for the Perovskite Phase of material before and after doping.
La0.9Ca0.1Co0.4Mo.6O3-δF0.7Tubular membrane carries out the oxygen permeability test under different temperatures.From test result In as can be seen that doping F elements can significantly improve Oxygen permeation flux of the material in middle low-temperature zone, reached in 550 DEG C of oxygen fluxes 0.38mlmin is arrived-1cm-2, it is adapted in oxygen separating and the application of film reaction field.
Embodiment 4
Material BaCo of the present invention is prepared with solid reaction process0.9Nb0.1O3-δF1Exemplified by, by the stoichiometric proportion of material by city The BaCO of purchase3, Co2O3, Nb2O5, and BaF2After powder mixing, ethanol is added, is placed in wet film 10h in ball mill, rotating speed 500rpm, then dried in still air, dry powder is calcined 5h in 850 DEG C of air atmospheres, it is polished to obtain Particle diameter is about 3 μm of BaCo0.9Nb0.1O3-δF1Powder.
Hollow-fibre membrane green compact are made by phase conversion method in powder, and it is 1 DEG C/min to control heating rate, and film green compact are existed 1100 DEG C of sintering cool to room temperature with 3 DEG C/min speed, produce hollow-fibre membrane after 5 hours.
By BaCo0.9Nb0.1O3-δF1Powder carries out X-ray diffraction test, it is found that it has complete Perovskite Phase structure, Obvious change does not occur for the Perovskite Phase of material before and after doping.
BaCo0.9Nb0.1O3-δF1Hollow-fibre membrane carries out the oxygen permeability test under different temperatures.From test result As can be seen that doping F elements can significantly improve Oxygen permeation flux of the material in middle low-temperature zone, reach in 550 DEG C of oxygen fluxes 1.22mlmin-1cm-2, it is adapted in oxygen separating and the application of film reaction field.We also investigate the material of the present invention simultaneously BaCo0.9Nb0.1O3-δF1The stability of Oxygen permeation at 600 DEG C.As shown in Figure 5, in 500h test process, the material exists Oxygen permeation flux is always held at 2.32mlmin at 600 DEG C-1cm-2Left and right.The Oxygen permeation process of this explanation material has fine Stability.
Embodiment 5
Material SrCo of the present invention is prepared with solid reaction process0.9Sc0.1O3-δF0.5Exemplified by, by the stoichiometric proportion of material by city The SrCO of purchase3, Co2O3, Sc2O3, and SrF2After powder mixing, ethanol is added, is placed in wet film 5h in ball mill, rotating speed 450rpm, then dried in still air, dry powder is calcined 6h in 950 DEG C of air atmospheres, it is polished to obtain Particle diameter is about 10 μm of SrCo0.9Sc0.1O3-δF0.5Powder.
Chip film green compact are made by single shaft platen press in powder, and it is 3 DEG C/min to control heating rate, by film green compact at 1150 DEG C Sintering cools to room temperature with 1 DEG C/min speed, produces fine and close chip film after 10 hours.
By SrCo0.9Sc0.1O3-δF0.5Powder carries out X-ray diffraction test, it is found that it has complete Perovskite Phase structure, Obvious change does not occur for the Perovskite Phase of material before and after doping.
SrCo0.9Sc0.1O3-δF0.5Chip film carries out the oxygen permeability test under different temperatures.Can be with from test result Find out, doping F elements can significantly improve Oxygen permeation flux of the material in middle low-temperature zone, reach in 500 DEG C of oxygen fluxes 0.23mlmin-1cm-2, it is adapted in oxygen separating and the application of film reaction field.We also investigate the material of the present invention simultaneously SrCo0.9Sc0.1O3-δF0.5The stability of Oxygen permeation at 550 DEG C.In 1000h test process, material oxygen at 550 DEG C Permeation flux is always held at 0.48mlmin-1cm-2Left and right.The Oxygen permeation process of this explanation material has good stability.
Embodiment 6
Material SrFe of the present invention is prepared with solid reaction process0.9Sc0.1O3-δF0.05Exemplified by, will by the stoichiometric proportion of material SrCO purchased in market3, Fe2O3, Sc2O3, and SrF2After powder mixing, ethanol is added, is placed in wet film 8h in ball mill, rotating speed 450rpm, then dried in still air, dry powder is calcined 6h in 950 DEG C of air atmospheres, it is polished to obtain Particle diameter is about 10 μm of SrFe0.9Sc0.1O3-δF0.05Powder.
Chip film green compact are made by single shaft platen press in powder, and it is 4 DEG C/min to control heating rate, by film green compact at 1170 DEG C Sintering cools to room temperature with 2 DEG C/min speed, produces fine and close chip film after 8 hours.
By SrFe0.9Sc0.1O3-δF0.05Powder carries out X-ray diffraction test, it is found that it has complete Perovskite Phase knot Structure, obvious change does not occur for the Perovskite Phase of material before and after doping.
SrFe0.9Sc0.1O3-δF0.05Chip film carries out the oxygen permeability test under different temperatures.Can from test result To find out, doping F elements can significantly improve Oxygen permeation flux of the material in middle low-temperature zone, reach in 500 DEG C of oxygen fluxes 0.13mlmin-1cm-2, it is adapted in oxygen separating and the application of film reaction field.We also investigate the material of the present invention simultaneously SrFe0.9Sc0.1O3-δF0.5The stability of Oxygen permeation at 550 DEG C.In 1000h test process, material oxygen at 550 DEG C Permeation flux is always held at 0.35mlmin-1cm-2Left and right.The Oxygen permeation process of this explanation material has good stability. We are also by SrFe0.9Sc0.1O3-δF0.05Chip film is used in catalytic partial oxidation of methane course of reaction, the methane at 600 DEG C Conversion ratio reaches 100%, and Oxygen permeation flux reaches 6mlmin-1cm-2, CO selectively reaches 100%.

Claims (8)

  1. A kind of 1. application of the Ca-Ti ore type film of Fluorin doped in oxygen separating.
  2. 2. application according to claim 1, it is characterised in that the Ca-Ti ore type film of described Fluorin doped, the formula of its material For AxA’1-xByB’1-yO3-δFγPerovskite crystal formation oxyfluoride, wherein δ is oxygen lattice defect number, A, A ' be Ce, Pr, Any one element in Nd, Ca, Sr, Ba or La；B, B ' is any in Co, Fe, Nb, Ta, Mo, W, Sc, Ti, Zr, Sn or Sb A kind of element；0≤x≤1,0≤y≤1；0<γ≤1.
  3. 3. application according to claim 2, it is characterised in that the Ca-Ti ore type film of described Fluorin doped is by following methods system Standby to obtain, it is comprised the following steps that：
    A. weigh raw material according to the stoichiometric proportion of material to be mixed, carry out dry mixture at roasting after well mixed Reason, membrane material is obtained after products therefrom grinding；
    B. the green compact of film are made by being molded for above-mentioned membrane material；After the green compact of film heat up and sintered in high temperature furnace, cooling is taken out, Produce film.
  4. 4. application according to claim 3, it is characterised in that the method mixed in step A is ball milling 3-10h, and rotating speed is 400-550rpm。
  5. 5. application according to claim 3, it is characterised in that sintering temperature in step A is 800-1200 DEG C, during roasting Between be 5-10h.
  6. 6. application according to claim 3, it is characterised in that the particle diameter of membrane material is 200nm-10 μ after being ground in step A m。
  7. 7. application according to claim 3, it is characterised in that described molding mode is that single shaft pressure, plasticity extrusion or phase turn Change method is molded.
  8. 8. application according to claim 3, it is characterised in that it is 1-5 DEG C/min that heating rate is sintered in step B, sintering temperature Spend for 1000-1300 DEG C, sintering time is 5-20 hours, and rate of temperature fall is 1-5 DEG C/min.
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CN101575210A (en) * 2009-06-22 2009-11-11 北京科技大学 Method for improving structural stability of BaCo0.7Fe0.2Nb0.1O3-Delta oxygen permeation membrane material

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